Chemoselective Hydrogenation of Nitroarenes Catalyzed by Molybdenum Sulphide Clusters
| Autor: | Rosa Llusar, Matthias Beller, Artem L. Gushchin, Elena Pedrajas, Kathrin Junge, Iván Sorribes, Yuliya A. Laricheva |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
sulfides
nitroarenes Reaction intermediate 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Inorganic Chemistry Nitrobenzene chemistry.chemical_compound Aniline molybdenum Organic chemistry clusters Physical and Theoretical Chemistry Substitution reaction 010405 organic chemistry Chemistry Ligand Organic Chemistry anilines 0104 chemical sciences Thiourea Yield (chemistry) hydrogenation |
| Popis: | Herein, we describe an atom efficient and general protocol for the chemoselective hydrogenation of nitroarenes to anilines catalyzed by well-defined diimino and diamino cubane-type Mo3S4 clusters. The novel diimino [Mo3S4Cl3(dnbpy)3]+ ([5]+) (dnbpy= 4,4'-dinonyl-2,2'-dipyridyl, L1) trinuclear complex was synthesized in high yields by simple ligand substitution reactions starting from the thiourea (tu) [Mo3S4(tu)8(H2O)]Cl4·4H2O (3) precursor. This strategy has also been successfully adapted for the isolation of the diamino [Mo3S4Cl3(dmen)3](BF4) ([6](BF4)), (dmen= N,N'-dimethylethylenediamine) salt. Applying these catalysts, high selectivity in the hydrogenation of functionalized nitroarenes has been accomplished. Over thirty anilines bearing synthetically functional groups have been synthesized in 70 to 99% yield. Notably, the integrity of the cluster core is preserved during catalysis. Based on kinetic studies on the hydrogenation of nitrobenzene and other potential reaction intermediates, the direct reduction to aniline is the preferential route. |
| Databáze: | OpenAIRE |
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